Phenanthrene compounds for organic electronic devices

ABSTRACT

The invention relates to specific phenanthrenes, the use of the compound in an electronic device, and an electronic device containing at least one of said compounds. The invention further relates to a method for producing the compound and a formulation and composition containing one or more of the compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of application Ser. No.15/783,333 filed Oct. 13, 2017, which is incorporated by reference inits entirety. Application Ser. No. 15/783,333 is a divisionalapplication of application Ser. No. 14/406,059 filed Dec. 5, 2014, whichis incorporated by reference in its entirety. Application Ser. No.14/406,059 is a national stage application (under 35 U.S.C. § 371) ofPCT/EP2013/001333, filed May 6, 2013, which claims benefit of GermanApplication No. 10 2012 011 335.8, filed Jun. 6, 2012, both of which areincorporated herein by reference in their entirety.

The present invention relates to novel organic compounds, to the use ofthe compound in an electronic device, and to an electronic devicecomprising at least one of the compounds. The present inventionfurthermore relates to a process for the preparation of the compoundsand to compositions and formulations and comprising at least one of thecompounds.

The development of functional compounds for use in electronic devices iscurrently the subject of intensive research. The aim here is, inparticular, the development of compounds with which improved propertiesof the electronic devices can be achieved in one or more relevantpoints, such as, for example, performance efficiency, lifetime or colourcoordinates of the emitted light.

In accordance with the present invention, the term electronic device istaken to mean, inter alia, organic integrated circuits (OICs), organicfield-effect transistors (OFETs), organic thin-film transistors (OTFTs),organic light-emitting transistors (OLETs), organic solar cells (OSCs),organic optical detectors, organic photoreceptors, organic field-quenchdevices (OFQDs), organic light-emitting electrochemical cells (OLECs),organic laser diodes (O-lasers) and organic electroluminescent devices(OLEDs).

Of particular interest is the provision of compounds for use in thelast-mentioned electronic devices referred to as OLEDs. The generalstructure and functional principle of OLEDs is known to the personskilled in the art and is described, inter alia, in U.S. Pat. Nos.4,539,507, 5,151,629, EP 0676461 and WO 1998/27136.

Regarding the performance data of OLEDs, further improvements are stillnecessary, in particular in view of broad commercial use, for example indisplay devices or as light sources. Of particular importance in thisconnection are the lifetime, the efficiency and the operating voltage ofthe OLEDs and the colour values achieved. In addition, it is desirablefor the compounds for use as functional materials in electronic devicesto have high thermal stability and a high glass-transition temperatureand to be sublimable without decomposition.

In this connection, there is, in particular, a need for alternativehole-transport materials. In the case of hole-transport materials inaccordance with the prior art, the voltage generally increases with thelayer thickness of the hole-transport layer. In practice, a greaterlayer thickness of the hole-transport layer would frequently bedesirable, but this frequently has the consequence of a higher operatingvoltage and worse performance data. In this connection, there is a needfor novel hole-transport materials which have high charge-carriermobility, so that thicker hole-transport layers having only a slightincrease in the operating voltage can be achieved.

The prior art discloses the use, in particular, of arylamine compoundsand carbazole compounds as hole-transport materials for OLEDs.

The application WO 2010/083871 discloses the use of dihydroacridinederivatives which are substituted by one or more arylamino groups asfunctional materials in OLEDs, preferably as hole-transport andhole-injection materials.

KR 2011047803 discloses phenanthrenes, which may be diamines ormonoamines, where the amine group in the case of the monoamine is notbonded via position 3 of the phenanthrene.

JP 1992321649 discloses aromatic tertiary amines which contain twoalkene groups. Also disclosed is a single compound which exhibits aphenanthrene which contains an amine group in position 3, where theamine is furthermore substituted by two aromatic groups which themselveseach contain an aklene group.

US 2008/0182129 discloses anthracenes which are substituted by amoraticamines, where the aromatic group may also be a phenanthrene.

WO 2011/136482 describes substituted phenanthrenes as charge-transportcompounds. The phenanthrenes disclosed herein are at least disubstitutedwhere both substituents contain an amine group.

However, there remains a need for novel hole-transport andhole-injection materials for use in OLEDs. In particular, there is aneed for materials with which the above-mentioned, highly desiredimprovements in the performance data and properties of the OLEDs can beachieved.

There is likewise a need for novel matrix materials for use in OLEDs andin other electronic devices. In particular, there is a need for matrixmaterials for phosphorescent dopants and for matrix materials formixed-matrix systems which preferably result in good efficiency, a longlifetime and a low operating voltage of the electronic devices.

The present invention is thus based on the object of providing compoundswhich are suitable for use in electronic devices, such as, for example,OLEDs, and which can be employed, in particular, as hole-transportmaterials and/or as hole-injection materials and/or as light-emittingmaterials and/or as matrix materials.

In the context of the present invention, it has surprisingly been foundthat compounds of the formula (1) indicated below are highly suitablefor the above-mentioned uses.

The invention thus relates to a compound of a formula (1)

where the following applies to the symbols and indices used:

-   X is on each occurrence, identically or differently, N and CR¹,    where a maximum of 2 of the X may be equal to N;-   L is a single bond or a divalent aryl or heteroaryl group having 12    to 40 ring atoms, which may be substituted by one or more radicals    R², where, if L is a single bond, the nitrogen is bonded directly to    position 3 of the phenanthrene, where L is preferably a single bond;-   Ar¹, Ar²    -   is on each occurrence, identically or differently, an aromatic        or heteroaromatic ring or an aromatic or heteroaromatic ring        system having 5 to 40 aromatic ring atoms, which may be        substituted by one or more radicals R⁴, where, if both Ar¹ and        also Ar² are phenyl radicals, at least one R⁴ on the phenyl        radicals is not equal to H and this at least one radical R⁴        preferably itself contains one or more aromatic or        heteroaromatic rings, where it is preferred for both groups Ar¹        and Ar² each to contain at least two aromatic or heteroaromatic        rings and where the rings may be bridged within Ar¹ and/or the        rings may be bridged within Ar² in such a way that non-aromatic        or non-heteroaromatic rings form, where it is very preferred for        the rings not to be bridged;-   R¹ is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, C(═O)R², CN, Si(R²)₃, NO₂, P(═O)(R²)₂, S(═O)R², S(═O)₂R², a    straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C    atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group    having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20    C atoms, where the above-mentioned groups may each be substituted by    one or more radicals R² and where one or more CH₂ groups in the    above-mentioned groups may be replaced by    -   —R²C═CR²—, —C≡C—, Si(R²)₂, C═O, C═S,    -   C═NR², —C(═O)O—, —C(═O)NR²—, P(═O)(R²), —O—, —S—, SO or SO₂ and        where one or more H atoms in the above-mentioned groups may be        replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic ring        system having 6 to 30 aromatic ring atoms, which may in each        case be substituted by one or more radicals R², where two or        more radicals R¹ may be linked to one another and may form a        ring;-   R⁴ is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, C(═O)R², CN, Si(R²)₃, NR², NO₂, P(═O)(R²)₂, S(═O)R²,    S(═O)₂R², a straight-chain alkyl, alkoxy or thioalkyl group having 1    to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl    group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2    to 20 C atoms, where the above-mentioned groups may each be    substituted by one or more radicals R² and where one or more CH₂    groups in the above-mentioned groups may be replaced by    -   —R²C═CR²—, —C≡C—, Si(R²)₂, C═O, C═S,    -   C═NR², —C(═O)O—, —C(═O)NR²—, P(═O)(R²), —O—, —S—, SO or SO₂ and        where one or more H atoms in the above-mentioned groups may be        replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic ring        system having 6 to 30 aromatic ring atoms, which may in each        case be substituted by one or more radicals R², where two or        more radicals R⁴ may be linked to one another and may form a        ring;-   R² is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, C(═O)R³, CN, Si(R³)₃, NO₂, P(═O)(R³)₂, S(═O)R³, S(═O)₂R³, a    straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C    atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group    having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20    C atoms, where the above-mentioned groups may each be substituted by    one or more radicals R³ and where one or more CH₂ groups in the    above-mentioned groups may be replaced by —R³C═CR³—, —C≡C—, Si(R³)₂,    C═O, C═S, C═NR³, —C(═O)O—, —C(═O)NR³—, P(═O)(R³), —O—, —S—, SO or    SO₂ and where one or more H atoms in the above-mentioned groups may    be replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or    heteroaromatic ring system having 5 to 30 aromatic ring atoms, which    may in each case be substituted by one or more radicals R³, or an    aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms,    which may be substituted by one or more radicals R³, where two or    more radicals R² may be linked to one another and may form a ring;-   R³ is on each occurrence, identically or differently, H, D, F or an    aliphatic, aromatic or heteroaromatic organic radical having 1 to 20    C atoms, in which, in addition, one or more H atoms may be replaced    by D or F; two or more substituents R³ here may be linked to one    another and may form a ring;    with the proviso that the compound of the formula (1), besides the    phenanthrene, contains no further condensed aromatic or    heteroaromatic ring having more than 10 ring atoms and    with the proviso that the radicals R¹ on the phenanthrene in    formula (1) contain no further amine groups.

The numbering on the phenanthrene here is defined as follows.

An aryl group in the sense of this invention contains 6 to 60 aromaticring atoms; a heteroaryl group in the sense of this invention contains 5to 60 aromatic ring atoms, at least one of which is a heteroatom. Theheteroatoms are preferably selected from N, O and S. This represents thebasic definition. If other preferences are indicated in the descriptionof the present invention, for example with respect to the number ofaromatic ring atoms or the heteroatoms present, these apply.

An aryl group or heteroaryl group here is taken to mean either a simplearomatic ring, i.e. benzene, or a simple heteroaromatic ring, forexample pyridine, pyrimidine or thiophene, or a condensed (annellated)aromatic or heteroaromatic polycycle, for example naphthalene,phenanthrene, quinoline or carbazole. A condensed (annellated) aromaticor heteroaromatic polycycle in the sense of the present applicationconsists of two or more simple aromatic or heteroaromatic ringscondensed with one another.

An aryl or heteroaryl group, which may in each case be substituted bythe above-mentioned radicals and which may be linked to the aromatic orheteroaromatic ring system via any desired positions, is taken to mean,in particular, groups derived from benzene, naphthalene, anthracene,phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene,benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene,furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole,isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine,phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine,naphthyridine, azacarbazole, benzocarboline, phenanthroline,1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine andbenzothiadiazole.

An aryloxy group in accordance with the definition of the presentinvention is taken to mean an aryl group, as defined above, which isbonded via an oxygen atom. An analogous definition applies toheteroaryloxy groups.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 5 to 60 aromatic ring atoms, at least one ofwhich is a heteroatom. The heteroatoms are preferably selected from N, Oand/or S. An aromatic or heteroaromatic ring system in the sense of thisinvention is intended to be taken to mean a system which does notnecessarily contain only aryl or heteroaryl groups, but instead inwhich, in addition, a plurality of aryl or heteroaryl groups may beconnected by a non-aromatic unit (preferably less than 10% of the atomsother than H), such as, for example, an sp³-hybridised C, Si, N or Oatom, an sp²-hybridised C or N atom or an sp-hybridised C atom. Thus,for example, systems such as 9,9′-spirobifluorene, 9,9′-diarylfluorene,triarylamine, diaryl ether, stilbene, etc., are also intended to betaken to be aromatic ring systems in the sense of this invention, as aresystems in which two or more aryl groups are connected, for example, bya linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group.Furthermore, systems in which two or more aryl or heteroaryl groups arelinked to one another via single bonds are also taken to be aromatic orheteroaromatic ring systems in the sense of this invention, such as, forexample, systems such as biphenyl, terphenyl or diphenyltriazine.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may in each case also be substituted by radicals as definedabove and which may be linked to the aromatic or heteroaromatic groupvia any desired positions, is taken to mean, in particular, groupsderived from benzene, naphthalene, anthracene, benzanthracene,phenanthrene, benzophenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene,spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene,cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, indolocarbazole, indenocarbazole,pyridine, quinoline, isoquinoline, acridine, phenanthridine,benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,phenothiazine, phenoxazine, pyrazole, indazole, imidazole,benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole,pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine,benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene,2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole, or combinations ofthese groups.

For the purposes of the present invention, a straight-chain alkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, inwhich, in addition, individual H atoms or CH₂ groups may be substitutedby the groups mentioned above under the definition of the radicals, ispreferably taken to mean the radicals methyl, ethyl, n-propyl, i-propyl,n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl,cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl,cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl,pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl,pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl,octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl oroctynyl. An alkoxy or thioalkyl group having 1 to 40 C atoms ispreferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy,i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy,2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy,n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy,2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio,i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio,n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio,cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio,trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio,ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio,hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio,octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio,pentynylthio, hexynylthio, heptynylthio or octynylthio.

The formulation that two or more radicals may form a ring with oneanother is, for the purposes of the present description, intended to betaken to mean, inter alia, that the two radicals are linked to oneanother by a chemical bond. This is illustrated by the following scheme:

Furthermore, however, the above-mentioned formulation is also intendedto be taken to mean that, in the case where one of the two radicalsrepresents hydrogen, the second radical is bonded at the position towhich the hydrogen atom was bonded, with formation of a ring. This isintended to be illustrated by the following scheme:

For the purposes of the present invention, preference is given to thecompound of the general formula (2)

where the above definitions apply to the symbols.

For the purposes of the present invention, great preference is given toa compound of the general formula (3)

A furthermore preferred embodiment of the present invention is thecompound of the general formula (4), where the symbols are defined asindicated above.

For the purposes of the present invention, preference is furthermoregiven to the compound of the general formula (4a), where the symbols aredefined as indicated above and the preferred embodiments mentionedelsewhere also apply to the formula (4a). Thus, for example, in aparticularly preferred embodiment of the present invention, L in thecompound of the present formula is a single bond and the groups Ar¹ andAr² very particularly preferably each contain at least two aryl orheteroaryl groups.

For the purposes of the present invention, preference is furthermoregiven to a compound of the general formula (4b)

where

Q is on each occurrence, identically or differently, CR⁴ or N;

and where the above definitions and the preferred embodiments thereofapply to the other symbols.

For the purposes of the present invention, preference is furthermoregiven to a compound of the general formula (5)

where

Q is on each occurrence, identically or differently, CR⁴ or N;

and where the above definitions and the preferred embodiments thereofapply to the other symbols.

In a very preferred embodiment, the present invention relates to acompound of the general formula (6)

where the above definitions and the preferred embodiments thereof applyto the symbils and indices used.

Particular preference is given to a compound of the general formula (7)

In a further very particularly preferred embodiment of the presentinvention, at least 4 of the 5 Q in each of the two rings are equal toCR⁴, very particularly preferably all Q are equal to CR⁴.

As already described above, the compound of the formula (1), besides thephenanthrene, contains no further condensed aromatic or heteroaromaticring having more than 10 ring atoms. Consequently, the substituents Ar¹and Ar² and the rings A and B do not represent condensed aromatic orheteroaromatic ring systems having more than 10 ring atoms.

It is preferred for at least one of the radicals Ar¹ and Ar² or A and Bin formula (1) to contain more than one ring. It is very preferred forboth radicals Ar¹ and Ar² or A and B to contain at least 2 or morerings.

For the purposes of the present invention, preference is furthermoregiven to a compound of the general formula (1), characterised in that itcontains in total at least 26, very preferably in total at least 32,very particularly preferably in total at least 38 and especiallypreferably in total at least 44 ring atoms.

In an especially preferred embodiment of the present invention, thecompound of the formula (1) to (7) does not contain an aromatic orheteroaromatic group or an aromatic or heteroaromatic ring system in anyof the radicals R¹ bonded directly to the phenanthrene, where it is evenmore preferred for the compound of the formulae (1) to (7) to containonly one amine group. This results in particularly highly suitablecompounds for use in organic electronic and especially in organicelectroluminescent devices.

Particularly preferred aromatic and heteroaromatic units as groups Ar¹and Ar² are represented by the following formulae (8) to (100):

where the dashed line represents the bonding position and where thestructures may be substituted by one or more radicals R⁴, and R⁴ isdefined as indicated above.

In a preferred embodiment, L is an aromatic ring system selected fromthe group consisting of biphenylenes, terphenylenes and the compounds ofthe following formula (101a) and (101b)

where Y is equal to C(R²)₂, NR², O, Si(R²)₂ and S, preferably C(R²)₂,NR², O and S, very preferably C(R²)₂, NR² and 0 and especiallypreferably C(R²)₂ and NR², and where R² is defined as indicated above.

In a very preferred embodiment, L is a single bond, i.e. the nitrogenatom is bonded directly to the phenanthrene in position 3 via a singlebond.

In an especially preferred embodiment, the present inventions relates toa compound of the formula (1), characterised in that it contains onlyone amine group, so that the compounds of the formula (1) areconsequently monoamines.

Examples of compounds according to the invention are depicted in thefollowing table.

formula (102)

formula (103)

formula (104)

formula (105)

formula (106)

formula (107)

formula (108)

formula (109)

formula (110)

formula (111)

formula (112)

formula (113)

formula (114)

formula (115)

formula (116)

formula (117)

formula (118)

formula (119)

formula (120)

formula (121)

formula (122)

formula (123)

formula (124)

formula (125)

formula (126)

formula (127)

formula (128)

formula (129)

formula (130)

formula (131)

formula (132)

formula (133)

formula (134)

formula (135)

formula (136)

formula (137)

formula (138)

formula (139)

formula (140)

formula (141)

formula (142)

formula (143)

formula (144)

formula (145)

formula (146)

formula (147)

formula (148)

formula (149)

formula (150)

formula (151)

formula (152)

formula (153)

formula (154)

formula (155)

formula (156)

formula (157)

formula (158)

formula (159)

formula (160)

formula (161)

formula (162)

formula (163)

formula (164)

formula (165)

formula (166)

formula (167)

formula (168)

formula (169)

formula (170)

formula (171)

formula (172)

formula (173)

formula (174)

formula (175)

formula (176)

formula (177)

formula (178)

formula (179)

formula (180)

formula (181)

formula (182)

formula (183)

formula (184)

formula (185)

formula (186)

formula (187)

formula (188)

formula (189)

formula (190)

formula (191)

formula (192)

formula (193)

formula (194)

formula (195)

formula (196)

formula (197)

formula (198)

formula (199)

formula (200)

formula (201)

formula (202)

formula (203)

formula (204)

formula (205)

formula (206)

formula (207)

formula (208)

formula (209)

formula (210)

formula (211)

formula (212)

formula (213)

formula (214)

formula (215)

formula (216)

formula (217)

formula (218)

formula (219)

formula (220)

formula (221)

formula (222)

The compounds according to the invention can be synthesised by processesand reaction types known from the prior art, for example halogenation,Buchwald coupling and Suzuki coupling.

A preferred process for the preparation of the compounds according tothe invention starts from the basic structures depicted as startingmaterials in Scheme 1. These are in some cases commercially available,in other cases they can be prepared in a few synthetic steps fromsimple, commercially available compounds.

Scheme 1 below shows a preferred synthetic route for the preparation ofthe compounds according to the invention. For the synthesis of thecompounds according to the invention, on the phenanthrene compound A isreacted with an amine B of the formula Ar²—NH—Ar¹ in a Buchwald coupling

Another preferred synthetic route for the preparation of the compoundsaccording to the invention is depicted in Scheme 2. The synthetic routecomprises two coupling reactions: firstly, the the phenanthrene compoundA is reacted with an amine C of the formula Ar²—NH₂ in a first Buchwaldcoupling. Finally, a second Buchwald coupling is carried out with acompound D, for example with a bromoaryl compound.

The coupling reactions here are preferably Buchwald couplings.

The synthesis of the starting compounds (A) presents the person skilledin the art with no difficulties. They can be prepared, for example, byconversion of acetyl compounds into amines and subsequent conversioninto halides by means of the Sandmayer reaction. Examples in thisrespect are disclosed below.

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, chlorine, boronic acid or boronic acid ester, can beused as monomers for the generation of corresponding oligomers,dendrimers or polymers. The oligomerisation or polymerisation herepreferably takes place via the halogen functionality or the boronic acidfunctionality.

The present invention thus furthermore relates to a process for thepreparation of compounds of the formula (1) which is characterised inthat the process takes place either in accordance with Scheme 1 or inaccordance with Scheme 2.

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, chlorine, boronic acid or boronic acid ester, can beused as monomers for the generation of corresponding oligomers,dendrimers or polymers. Suitable reactive leaving groups are, forexample, bromine, iodine, chlorine, boronic acids, boronic acid esters,amines, alkenyl or alkynyl groups containing a terminal C—C double bondor C—C or triple bond respectively, oxiranes, oxetanes, groups whichundergo a cycloaddition, for example a 1,3-dipolar cycloaddition, suchas, for example, dienes or azides, carboxylic acid derivatives, alcoholsand silanes.

The invention therefore furthermore relates to oligomers, polymers ordendrimers containing one or more compounds of the formula (1), wherethe bond(s) to the polymer, oligomer or dendrimer may be localised atany desired positions in formula (1) which are substituted by R¹ or R².Depending on the linking of the compound of the formula (1), thecompound is part of a side chain of the oligomer or polymer or part ofthe main chain. An oligomer in the sense of this invention is taken tomean a compound which is built up from at least three monomer units. Apolymer in the sense of the invention is taken to mean a compound whichis built up from at least ten monomer units. The polymers, oligomers ordendrimers according to the invention may be conjugated, partiallyconjugated or non-conjugated. The oligomers or polymers according to theinvention may be linear, branched or dendritic. In the structures linkedin a linear manner, the units of the formula (1) may be linked directlyto one another or they may be linked to one another via a divalentgroup, for example via a substituted or unsubstituted alkylene group,via a heteroatom or via a divalent aromatic or heteroaromatic group. Inbranched and dendritic structures, three or more units of the formula(1) may, for example, be linked via a trivalent or polyvalent group, forexample via a trivalent or polyvalent aromatic or heteroaromatic group,to give a branched or dendritic oligomer or polymer.

The same preferences as described above for compounds of the formula (1)apply to the recurring units of the formula (1) in oligomers, dendrimersand polymers.

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Suitable and preferred comonomers are selected from fluorenes(for example in accordance with EP 842208 or WO 2000/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 2006/061181), para-phenylenes (for example in accordance with WO1992/18552), carbazoles (for example in accordance with WO 2004/070772or WO 2004/113468), thiophenes (for example in accordance with EP1028136), dihydrophenanthrenes (for example in accordance with WO2005/014689 or WO 2007/006383), cis- and trans-indenofluorenes (forexample in accordance with WO 2004/041901 or WO 2004/113412), ketones(for example in accordance with WO 2005/040302), phenanthrenes (forexample in accordance with WO 2005/104264 or WO 2007/017066) or also aplurality of these units. The polymers, oligomers and dendrimers usuallyalso contain further units, for example emitting (fluorescent orphosphorescent) units, such as, for example, vinyltriarylamines (forexample in accordance with WO 2007/068325) or phosphorescent metalcomplexes (for example in accordance with WO 2006/003000), and/orcharge-transport units, in particular those based on triarylamines.

The polymers, oligomers and dendrimers according to the invention haveadvantageous properties, in particular long lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers according to the invention are generallyprepared by polymerisation of one or more types of monomer, at least onemonomer of which results in recurring units of the formula (1) in thepolymer. Suitable polymerisation reactions are known to the personskilled in the art and are described in the literature. Particularlysuitable and preferred polymerisation reactions which result in C—C orC—N links are the following:

(A) SUZUKI polymerisation;

(B) YAMAMOTO polymerisation;

(C) STILLE polymerisation; and

(D) HARTWIG-BUCHWALD polymerisation.

The way in which the polymerisation can be carried out by these methodsand the way in which the polymers can then be separated off from thereaction medium and purified is known to the person skilled in the artand is described in detail in the literature, for example in WO2003/048225, WO 2004/037887 and WO 2004/037887.

The present invention thus also relates to a process for the preparationof the polymers, oligomers and dendrimers according to the invention,which is characterised in that they are prepared by SUZUKIpolymerisation, YAMAMOTO polymerisation, STILLE polymerisation orHARTWIG-BUCHWALD polymerisation. The dendrimers according to theinvention can be prepared by processes known to the person skilled inthe art or analogously thereto. Suitable processes are described in theliterature, such as, for example, in Frechet, Jean M. J.; Hawker, CraigJ., “Hyperbranched polyphenylene and hyperbranched polyesters: newsoluble, three-dimensional, reactive polymers”, Reactive & FunctionalPolymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “Thesynthesis and characterization of dendritic molecules”, MaterialsScience and Technology (1999), 20 (Synthesis of Polymers), 403-458;Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995),272(5), 62-6; WO 2002/067343 A1 and WO 2005/026144 A1.

For the processing of the compounds according to the invention from theliquid phase, for example by spin coating or by printing processes,formulations of the compounds according to the invention are necessary.These formulations can be, for example, solutions, dispersions ormini-emulsions. It may be preferred to use mixtures of two or moresolvents for this purpose. Suitable and preferred solvents are, forexample, toluene, phenoxytoluene, anisole, o-, m- or p-xylene, methylbenzoate, dimethylanisole, mesitylene, tetralin, veratrol, THF,methyl-THF, THP, chlorobenzene, dioxane or mixtures of these solvents.

The invention therefore furthermore relates to a formulation, inparticular a solution, dispersion or mini-emulsion, comprising at leastone compound of the formula (1) or at least one polymer, oligomer ordendrimer containing at least one unit of the formula (1), and at leastone solvent, preferably an organic solvent. The way in which solutionsof this type can be prepared is known to the person skilled in the artand is described, for example, in WO 2002/072714, WO 2003/019694 and theliterature cited therein.

The compounds according to the invention can be employed as compositionswith other organically functional materials which are used in electronicdevices. A multiplicity of possible organically functional materials(often also called organic semiconductors) are known to the personskilled in the art here. The present invention therefore also relates toa composition comprising one or more compound according to the inventionand at least one further organically functional material selected fromthe group consisting of fluorescent emitters, phosphorescent emitters,host materials, matrix materials, electron-transport materials,electron-injection materials, hole-conductor materials, hole-injectionmaterials, electron-blocking materials and hole-blocking materials.

The compounds according to the invention are suitable for use inelectronic devices, in particular in organic electroluminescent devices(OLEDs). Depending on the substitution, the compounds are employed invarious functions and layers.

The invention therefore furthermore relates to the use of the compoundsof the formula (1) in electronic devices and to electronic devicesthemselves which comprise one or more compounds of the formula (1). Theelectronic devices here are preferably selected from the groupconsisting of organic integrated circuits (OICs), organic field-effecttransistors (OFETs), organic thin-film transistors (OTFTs), organiclight-emitting transistors (OLETs), organic solar cells (OSCs), organicoptical detectors, organic photoreceptors, organic field-quench devices(OFQDs), organic light-emitting electrochemical cells (OLECs), organiclaser diodes (O-lasers) and particularly preferably organicelectroluminescent devices (OLEDs).

The invention relates, as already stated above, to electronic devicescomprising at least one compound of the formula (1). The electronicdevices here are preferably selected from the devices mentioned above.Particular preference is given to organic electroluminescent devices(OLEDs) comprising anode, cathode and at least one emitting layer,characterised in that at least one organic layer, which can be anemitting layer, a hole-transport layer or another layer, comprises atleast one compound of the formula (1).

Apart from cathode, anode and the emitting layer, the organicelectroluminescent device may also comprise further layers. These areselected, for example, from in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, electron-blocking layers,exciton-blocking layers, interlayers, charge-generation layers (IDMC2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K.Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL DeviceHaving Charge Generation Layer) and/or organic or inorganic p/njunctions. However, it should be pointed out that each of these layersdoes not necessarily have to be present and the choice of layers isalways dependent on the compounds used and in particular also on whetherthe electroluminescent device is fluorescent or phosphorescent.

The organic electroluminescent device according to the invention maycomprise a plurality of emitting layers. In this case, these emissionlayers particularly preferably have in total a plurality of emissionmaxima between 380 nm and 750 nm, resulting overall in white emission,i.e. various emitting compounds which are able to fluoresce orphosphoresce and which emit blue or yellow or orange or red light areused in the emitting layers. Especial preference is given to three-layersystems, i.e. systems having three emitting layers, where the threelayers exhibit blue, green and orange or red emission (for the basicstructure see, for example, WO 2005/011013). The compounds according tothe invention may be present in a hole-transport layer, an emittinglayer and/or in another layer in such devices. It should be noted that,for the generation of white light, an emitter compound used individuallywhich emits in a broad wavelength range may also be suitable instead ofa plurality of emitter compounds emitting in colour.

It is preferred in accordance with the invention for the compound of theformula (1) to be employed in an electronic device comprising one ormore phosphorescent dopants. The compound here can be used in variouslayers, preferably in a hole-transport layer, a hole-injection layer orin an emitting layer. However, the compound of the formula (1) can alsobe employed in accordance with the invention in an electronic devicecomprising one or more fluorescent dopants.

If the compound of the formula (1) is employed as hole-transportmaterial in a hole-transport layer, a hole-injection layer or anelectron-blocking layer, the compound can be employed as pure material,i.e. in a proportion of 100%, in the hole-transport layer, or it can beemployed in combination with one or more further compounds. According toa preferred embodiment, the organic layer comprising the compound of theformula (1) then additionally comprises one or more p-dopants. Thep-dopants employed in accordance with the present invention arepreferably organic electron-acceptor compounds which are able to oxidiseone or more of the other compounds of the mixture.

Particularly preferred embodiments of p-dopants are the compoundsdisclosed in WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP1722602, EP 2045848, DE 102007031220, U.S. Pat. Nos. 8,044,390,8,057,712, WO 2009/003455, WO 2010/094378, WO 2011/120709, US2010/0096600 and WO 2012/095143.

In a further preferred embodiment of the invention, the compound of theformula (1) is used as hole-transport material in combination with ahexaazatriphenylene derivative, as described in US 2007/0092755. Thehexaazatriphenylene derivative here is particularly preferably employedin a separate layer.

Particularly preferred p-dopants are quinodimethane compounds,azaindenofluorenediones, azaphenalenes, azatriphenylenes, 12, metalhalides, preferably transition-metal halides, metal oxides, preferablymetal oxides containing at least one transition metal or a metal of the3rd main group, and transition-metal complexes, preferably complexes ofCu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atomas bonding site. Preference is furthermore given to transition-metaloxides as dopants, preferably oxides of rhenium, molybdenum andtungsten, particularly preferably Re₂O₇, MoO₃, WO₃ and ReO₃.

Preferred p-dopants are furthermore the following compounds:

The p-dopant in hole-transport layer is preferably present in aconcentration of 0.1 to 20% by vol, very preferably 0.5 to 12% by vol,particularly preferably 1 to 8% by vol and very particularly preferably2 to 6% by vol.

The hole-transport layer preferably has a thickness of 5 to 50 nm,particularly preferably 10 to 40 nm.

The term phosphorescent dopants typically encompasses compounds in whichthe light emission takes place through a spin-forbidden transition, forexample a transition from an excited triplet state or a state having arelatively high spin quantum number, for example a quintet state.

Suitable phosphorescent dopants (=triplet emitters) are, in particular,compounds which emit light, preferably in the visible region, onsuitable excitation and in addition contain at least one atom having anatomic number greater than 20, preferably greater than 38 and less than84, particularly preferably greater than 56 and less than 80. Thephosphorescent emitters used are preferably compounds which containcopper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium,iridium, palladium, platinum, silver, gold or europium, in particularcompounds which contain iridium, platinum or copper.

All luminescent iridium, platinum or copper complexes are regarded asphosphorescent compounds in the sense of the present invention.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/019373 and US2005/0258742. In general, all phosphorescent complexes as are used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescent devices are suitable. The person skilled in the artwill also be able, without inventive step, to employ furtherphosphorescent complexes in combination with the compounds of theformula (1) in organic electroluminescent devices.

Explicit examples of suitable phosphorescent emitter compounds arefurthermore revealed by the following table.

In a preferred embodiment of the invention, the compounds of the formula(1) are employed as hole-transport material. The compounds are thenpreferably employed in a hole-transport layer and/or in a hole-injectionlayer. A hole-injection layer in the sense of this invention is a layerwhich is directly adjacent to the anode. A hole-transport layer in thesense of this invention is a layer which is located between thehole-injection layer and the emission layer. The hole-transport layermay be directly adjacent to the emission layer. If the compounds of theformula (1) are used as hole-transport material or as hole-injectionmaterial, it may be preferred for them to be doped withelectron-acceptor compounds, for example with F₄-TCNQ or with compoundsas described in EP 1476881 or EP 1596445. In a further preferredembodiment of the invention, a compound of the formula (I) is used ashole-transport material in combination with a hexaazatriphenylenederivative, as described in US 2007/0092755. The hexaazatriphenylenederivative here is particularly preferably employed in a separate layer.

If the compound of the formula (1) is employed as hole-transportmaterial in a hole-transport layer, the compound can be employed as purematerial, i.e. in a proportion of 100%, in the hole-transport layer, orit can be employed in combination with one or more further compounds inthe hole-transport layer.

In a further embodiment of the present invention, the compounds of theformula (1) are employed as emitting materials. To this end, thecompounds are preferably employed in an emission layer. Besides at leastone of the compounds of the formula (1), the emission layer furthermorecomprises at least one host material. The person skilled in the art willbe able to make a selection from the known host materials withoutdifficulties and without being inventive.

In a further embodiment of the present invention, the compounds of theformula (1) are employed as matrix material in combination with one ormore dopants, preferably phosphorescent dopants.

A dopant in a system comprising a matrix material and a dopant is takento mean the component whose proportion in the mixture is the smaller.Correspondingly, a matrix material in a system comprising a matrixmaterial and a dopant is taken to mean the component whose proportion inthe mixture is the greater.

The proportion of the matrix material in the emitting layer in this caseis between 50.0 and 99.9% by vol., preferably between 80.0 and 99.5% byvol. and particularly preferably between 92.0 and 99.5% by vol. forfluorescent emitting layers and between 85.0 and 97.0% by vol. forphosphorescent emitting layers.

Correspondingly, the proportion of the dopant is between 0.1 and 50.0%by vol., preferably between 0.5 and 20.0% by vol. and particularlypreferably between 0.5 and 8.0% by vol. for fluorescent emitting layersand between 3.0 and 15.0% by vol. for phosphorescent emitting layers.

An emitting layer of an organic electroluminescent device may alsocomprise systems comprising a plurality of matrix materials(mixed-matrix systems) and/or a plurality of dopants. In this case too,the dopants are generally the materials whose proportion in the systemis the smaller and the matrix materials are the materials whoseproportion in the system is the greater. In individual cases, however,the proportion of an individual matrix material in the system may besmaller than the proportion of an individual dopant.

In a further preferred embodiment of the invention, the compounds of theformula (1) are used as a component of mixed-matrix systems. Themixed-matrix systems preferably comprise two or three different matrixmaterials, particularly preferably two different matrix materials. Oneof the two materials here is preferably a material havinghole-transporting properties and the other material is a material havingelectron-transporting properties. However, the desiredelectron-transporting and hole-transporting properties of themixed-matrix components may also be combined principally or completelyin a single mixed-matrix component, where the further mixed-matrixcomponent(s) fulfil other functions. The two different matrix materialshere may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1,particularly preferably 1:10 to 1:1 and very particularly preferably 1:4to 1:1. Mixed-matrix systems are preferably employed in phosphorescentorganic electroluminescent devices. More precise information onmixed-matrix systems is given, inter alia, in the application WO2010/108579.

The mixed-matrix systems may comprise one or more dopants, preferablyone or more phosphorescent dopants. In general, mixed-matrix systems arepreferably employed in phosphorescent organic electroluminescentdevices.

Particularly suitable matrix materials which can be used as matrixcomponents of a mixed-matrix system in combination with the compoundsaccording to the invention are selected from the preferred matrixmaterials for phosphorescent dopants indicated below or the preferredmatrix materials for fluorescent dopants, depending on what type ofdopant is employed in the mixed-matrix system.

Preferred phosphorescent dopants for use in mixed-matrix systems are thephosphorescent dopants shown in the above table.

The materials preferably employed in the relevant functions in thedevices according to the invention are indicated below.

Preferred fluorescent dopants are selected from the class of thearylamines. An arylamine or aromatic amine in the sense of thisinvention is taken to mean a compound which contains three substitutedor unsubstituted aromatic or heteroaromatic ring systems bonded directlyto the nitrogen. At least one of these aromatic or heteroaromatic ringsystems is preferably a condensed ring system, particularly preferablyhaving at least 14 aromatic ring atoms. Preferred examples thereof arearomatic anthracenamines, aromatic anthracenediamines, aromaticpyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromaticchrysenediamines. An aromatic anthracenamine is taken to mean a compoundin which one diarylamino group is bonded directly to an anthracenegroup, preferably in the 9-position. An aromatic anthracenediamine istaken to mean a compound in which two diarylamino groups are bondeddirectly to an anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediaminesare defined analogously thereto, where the diarylamino groups arepreferably bonded to the pyrene in the 1-position or in the1,6-position.

Suitable matrix materials, preferably for fluorescent dopants, besidesthe compounds according to the invention, are materials from variousclasses of substance. Preferred matrix materials are selected from theclasses of the oligoarylenes (for example2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP 676461 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, the oligoarylenevinylenes (for example DPVBior spiro-DPVBi in accordance with EP 676461), the polypodal metalcomplexes (for example in accordance with WO 2004/081017), thehole-conducting compounds (for example in accordance with WO2004/058911), the electron-conducting compounds, in particular ketones,phosphine oxides, sulfoxides, etc. (for example in accordance with WO2005/084081 and WO 2005/084082), the atropisomers (for example inaccordance with WO 2006/048268), the boronic acid derivatives (forexample in accordance with WO 2006/117052) or the benzanthracenes (forexample in accordance with WO 2008/145239). Particularly preferredmatrix materials are selected from the classes of the oligoarylenes,comprising naphthalene, anthracene, benzanthracene and/or pyrene oratropisomers of these compounds, the oligoarylenevinylenes, the ketones,the phosphine oxides and the sulfoxides. Very particularly preferredmatrix materials are selected from the classes of the oligoarylenes,comprising anthracene, benzanthracene, benzophenanthrene and/or pyreneor atropisomers of these compounds. An oligoarylene in the sense of thisinvention is intended to be taken to mean a compound in which at leastthree aryl or arylene groups are bonded to one another.

Preferred matrix materials for phosphorescent dopants, besides thecompounds according to the invention, are aromatic amines, in particulartriarylamines, for example in accordance with US 2005/0069729, carbazolederivatives (for example CBP, N,N-biscarbazolylbiphenyl) or compounds inaccordance with WO 2005/039246, US 2005/0069729, JP 2004/288381, EP1205527 or WO 2008/086851, bridged carbazole derivatives, for example inaccordance with WO 2011/088877 and WO 2011/128017, indenocarbazolederivatives, for example in accordance with WO 2010/136109 and WO2011/000455, azacarbazole derivatives, for example in accordance with EP1617710, EP 1617711, EP 1731584, JP 2005/347160, indolocarbazolederivatives, for example in accordance with WO 2007/063754 or WO2008/056746, ketones, for example in accordance with WO 2004/093207 orWO 2010/006680, phosphine oxides, sulfoxides and sulfones, for examplein accordance with WO 2005/003253, oligophenylenes, bipolar matrixmaterials, for example in accordance with WO 2007/137725, silanes, forexample in accordance with WO 2005/111172, azaboroles or boronic esters,for example in accordance with WO 2006/117052, triazine derivatives, forexample in accordance with WO 2010/015306, WO 2007/063754 or WO2008/056746, zinc complexes, for example in accordance with EP 652273 orWO 2009/062578, aluminium complexes, for example BAIq, diazasilole andtetraazasilole derivatives, for example in accordance with WO2010/054729, diazaphosphole derivatives, for example in accordance withWO 2010/054730, and aluminium complexes, for example BAIQ.

Suitable charge-transport materials, as can be used in thehole-injection or hole-transport layer or in the electron-transportlayer of the organic electroluminescent device according to theinvention, besides the compounds according to the invention, are, forexample, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007,107(4), 953-1010, or other materials as are employed in these layers inaccordance with the prior art.

The cathode of the organic electroluminescent device preferablycomprises metals having a low work function, metal alloys ormultilayered structures comprising various metals, such as, for example,alkaline-earth metals, alkali metals, main-group metals or lanthanoids(for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable arealloys comprising an alkali metal or alkaline-earth metal and silver,for example an alloy comprising magnesium and silver. In the case ofmultilayered structures, further metals which have a relatively highwork function, such as, for example, Ag or Al, can also be used inaddition to the said metals, in which case combinations of the metals,such as, for example, Ca/Ag, Mg/Ag or Ba/Ag, are generally used. It mayalso be preferred to introduce a thin interlayer of a material having ahigh dielectric constant between a metallic cathode and the organicsemiconductor. Suitable for this purpose are, for example, alkali metalfluorides or alkaline-earth metal fluorides, but also the correspondingoxides or carbonates (for example LiF, Li₂O, BaF₂, MgO, NaF, CsF,Cs₂CO₃, etc.). Furthermore, lithium quinolinate (LiQ) can be used forthis purpose. The layer thickness of this layer is preferably between0.5 and 5 nm.

The anode preferably comprises materials having a high work function.The anode preferably has a work function of greater than 4.5 eV vs.vacuum. Suitable for this purpose are on the one hand metals having ahigh redox potential, such as, for example, Ag, Pt or Au. On the otherhand, metal/metal oxide electrodes (for example Al/Ni/NiO_(x),Al/PtO_(x)) may also be preferred. For some applications, at least oneof the electrodes must be transparent or partially transparent in orderto facilitate either irradiation of the organic material (organic solarcell) or the coupling-out of light (OLED, O-LASER). Preferred anodematerials here are conductive mixed metal oxides. Particular preferenceis given to indium tin oxide (ITO) or indium zinc oxide (IZO).Preference is furthermore given to conductive, doped organic materials,in particular conductive doped polymers.

The device is appropriately (depending on the application) structured,provided with contacts and finally sealed, since the lifetime of thedevices according to the invention is shortened in the presence of waterand/or air.

In a preferred embodiment, the organic electroluminescent deviceaccording to the invention is characterised in that one or more layersare coated by means of a sublimation process, in which the materials areapplied by vapour deposition in vacuum sublimation units at an initialpressure of less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar.However, it is also possible here for the initial pressure to be evenlower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are coated by means of the OVPD(organic vapour phase deposition) process or with the aid of carrier-gassublimation, in which the materials are applied at a pressure of between10⁻⁵ mbar and 1 bar. A special case of this process is the OVJP (organicvapour jet printing) process, in which the materials are applieddirectly through a nozzle and are thus structured (for example M. S.Amold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, nozzle printing or offset printing, but particularlypreferably LITI (light induced thermal imaging, thermal transferprinting) or ink-jet printing. Soluble compounds of the formula (I) arenecessary for this purpose. High solubility can be achieved throughsuitable substitution of the compounds.

For the production of an organic electroluminescent device according tothe invention, it is furthermore preferred to apply one or more layersfrom solution and one or more layers by a sublimation process.

In accordance with the invention, the electronic devices comprising oneor more compounds of the formula (I) can be employed in displays, aslight sources in lighting applications and as light sources in medicaland/or cosmetic applications (for example light therapy).

Devices comprising the compounds of the formula (1) can be employed in avery versatile manner. Thus, for example, electroluminescent devicescomprising one or more compounds of the formula (1) can be employed indisplays for televisions, mobile telephones, computers and cameras.However, the devices can also be used in lighting applications.Furthermore, electroluminescent devices, for example in OLEDs or OLECs,comprising at least one of the compound of the formula (1) can beutilised for phototherapy in medicine or cosmetics. Thus, a large numberof diseases (psoriasis, atopic dermatitis, inflammation, acne, skincancer, etc.) or the prevention or reduction of skin wrinkling, skinreddening and skin ageing can be treated. Furthermore, thelight-emitting devices can be utilised in order to keep drinks, meals orfoods fresh or in order to sterilise equipment (for example medicalequipment).

The present invention therefore also relates to an electronic device,preferably an organic electroluminescent device, very preferably an OLEDor OLEC, comprising at least one compound according to the invention forphototherapeutic use in medicine, preferably for use for the treatmentof skin diseases, very preferably for use for the treatment ofpsoriasis, atopic dermatitis, neurodermatitis, skin cancer, inflammationof the skin, jaundice (icterus) and jaundice of the newborn.

The present invention furthermore relates to the use of an electronicdevice, preferably an organic electroluminescent device, very preferablyan OLED or OLEC, comprising at least one compound according to theinvention in cosmetics, preferably for the treatment of acne, skinreddening, for the treatment of skin ageing (anti-ageing), for thereduction of skin wrinkles and for the treatment of cellulite.

The compounds according to the invention and the organicelectroluminescent devices according to the invention are distinguishedby the following surprising advantages over the prior art:

-   1. The compounds according to the invention are very highly suitable    for use in a hole-transport layer or a hole-injection layer in    electronic devices, such as, for example, in organic    electroluminescent devices, in particular owing to their high hole    mobility.-   2. The compounds according to the invention have a relatively low    sublimation temperature, high temperature stability and high    oxidation stability and a high glass-transition temperature, which    is advantageous both for the processability, for example from    solution or from the gas phase, and also for use in electronic    devices.-   3. The use of the compounds according to the invention in electronic    devices, in particular employed as hole-transport or hole-injection    material, but also as light-emitting material, result in high    efficiencies, low operating voltages and in long lifetimes.

It should be pointed out that variations of the embodiments described inthe present invention fall within the scope of this invention. Eachfeature disclosed in the present invention can, unless explicitlyexcluded, be replaced by alternative features which serve the same, anequivalent or a similar purpose. Thus, each feature disclosed in thepresent invention is, unless stated otherwise, to be regarded as anexample of a generic series or as an equivalent or similar feature.

All features of the present invention can be combined with one anotherin any way, unless certain features and/or steps are mutually exclusive.This applies in particular to preferred features of the presentinvention. Equally, features of non-essential combinations can be usedseparately (and not in combination).

It should furthermore be pointed out that many of the features, and inparticular those of the preferred embodiments of the present invention,are themselves inventive and should not merely be regarded as part ofthe embodiments of the present invention. For these features,independent protection may be sought in addition or as an alternative toeach invention currently claimed.

The teaching on technical action disclosed with the present inventioncan be abstracted and combined with other examples.

The invention is explained in greater detail by the following examples,without wishing to restrict it thereby.

EXAMPLES

Materials

Materials HIL1, HIL2 (EP 0676461), H1 (WO 2008/145239), ETM1 (WO2005/053055), SEB1 (WO 2008/006449), LiQ and NPB are well known to theperson skilled in the art. Their properties and syntheses are known fromthe prior art. Compounds (1-9), (1-1), (1-11), (1-12), (2-6) (1-2) and(4-1) are according to the invention.

Example 1 Synthesis ofbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)phenanthren-3-ylamine (1-1)

Synthesis of Starting Material 3-bromophenanthrene

Synthesis of 3-aminophenanthrene

50 g (227 mmol) of 3-acetylphenenthrene and 63.8 ml of pyridine (790mmol) and 42 g (592 mmol) of hydroxylammonium chloride are dissolved in300 ml of EtOH. The batch is heated to 75° C. After reaction for 1 h,the batch is cooled. The mixture is subsequently partitioned betweenethyl acetate and water, the organic phase is washed three times withwater and dried over Na₂SO₄ and concentrated in a rotary evaporator. 300ml of polyphosphoric acid are carefully added to the concentratedsolution, and the mixture is heated at 75° C. for 1 h. The batch is thencooled to room temperature, and carefully poured with ice-water (300ml). The precipitated solid is filtered off with suction and rinsed withmethanol. Finally, 800 ml of MeOH and 70 ml of conc. HCl are added tothe solid. The reaction mixture is heated at the boil for 8 h. Themixture is subsequently neutralised using sodium hydroxide solutions,partitioned between etyl acetate and water, the organic phase is washedthree times with water and dried over Na₂SO₄ and evaporated in a rotaryevaporator. The residue was dried at 40° C. in vacuo. Yield 35.5 g (184mmol) (81% of theory)

Synthesis of 3-bromophenanthrene

30 g (155 mmol) of 3-aminophenanthrene and 36.7 g of CuBr₂ (155 mmol)are dissolved in 300 ml of dried acetonitrile. 40.4 ml of tert-butylnitrite (535 mmol) are added in portions at 0° C. The suspension isstirred for a further 1 h and then poured onto 400 ml of ice-water andstirred for about 20 min. The precipitated solid is filtered off withsuction, dissolved in dichloromethane and washed a number of times withwater. The organic phase is evaporated in a rotary evaporator andrecrystallised from toluene/heptane. Yield: 21.9 g (85 mmol) (55% oftheory)

Other halogenated phenanthrenes as starting compounds can be preparedanalogously.

Starting material 1 Starting material 2 Product Yield

CuI₂

45%

CuCl₂

50%Synthesis of Compound (1-1)

28.1 g (78 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amines,20.0 g (78 mol) of 3-bromophenanthrenes are dissolved in 600 ml oftoluene: The solution is degassed and saturated with N₂. 3.1 ml (3.11mmol) of a tri-tert-butylphosphine solution and 0.35 g (1.56 mmol) ofpalladium(II) acetate are then added, and 11.6 g of sodium tert-butoxide(116.7 mmol) are subsequently added. The reaction mixture is heated atthe boil under a protective atmosphere for 5 h. The mixture issubsequently partitioned between toluene and water, the organic phase iswashed three times with water and dried over Na₂SO₄ and evaporated in arotary evaporator. After filtration of the crude product through silicagel with toluene, the residue which remains is recrystallised fromheptane/toluene and finally sublimed in a high vacuum, purity is 99.9%(HPLC). The yield of compound (1-1) is 29.6 g (71% of theory).

Examples 2-12 Synthesis of Compounds (1-2) to (1-12)

The following compounds (1-2) to (1-12) are also prepared analogously tothe synthesis of compound (1-1) described in Example 1.

Starting material 1 Starting material 2 Product Yield 1-2 

78% 1-3 

82% 1-4 

88% 1-5 

67% 1-6 

76% 1-7 

80% 1-8 

75% 1-9 

70% 1-10

67% 1-11

72% 1-12

65%

The following comparative compounds (HTMV1) to (HTMV3) and (HTMV6) to(HTMV7) are also prepared analogously to the synthesis of compound (1-1)described in Example 1.

Starting material 1 Starting material 2 Product HTMV1

HTMV2

HTMV3

HTMV6

HTMV7

Examples 13 Synthesis of the CompoundN*4′-biphenyl-4-yl-N*4′*-dibenzofuran-4-yl-N*4-phenanthren-3-yl-N*4*-phenylbiphenyl-4,4′-damine(2-1)

10 g of phenanthren-3-ylphenylamines (37 mmol), 21 g. ofbiphenyl-4-yl-(4′-bromobiphenyl-4-yl)dibenzofuran-4-ylamines (37 mol)are dissolved in 500 ml of toluene: The solution is degassed andsaturated with N₂. 1.5 ml (1.5 mmol) of a tri-tert-butylphosphinesolution and 0.17 g (0.74 mmol) of palladium(II) acetate are then added,and 5.6 g of sodium tert-butoxide (56 mmol) are subsequently added. Thereaction mixture is heated at the boil under a protective atmosphere for3 h. The mixture is subsequently partitioned between toluene and water,the organic phase is washed three times with water and dried over Na₂SO₄and evaporated in a rotary evaporator. After filtration of the crudeproduct through silica gel with toluene, the residue which remains isrecrystallised from heptane/toluene and finally sublimed in a highvacuum, purity is 99.9% (HPLC). The yield is 16.8 g (60% of theory).

Examples 14-18 Synthesis of Compounds (2-2) to (2-6)

The following compounds (2-2) to (2-6) are also prepared analogously tothe synthesis of compound (2-1) described in Example 13.

Starting material 1 Startinh material 2 2-2

2-3

2-4

2-5

2-6

Product Yield 2-2

55% 2-3

62% 2-4

65% 2-5

65% 2-6

60%

The comparative compound (HTMV5) is also prepared analogously to thesynthesis of compound (2-1) described in Example 13.

Starting Starting material 1 material 2 Product HTMV5

Examples 19 Synthesis of the Compoundbiphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenanthren-3-yl-9H-fluoren-2-yl)amine(3-1)

3-(7-Bromo-9,9-dimethyl-9H-fluoren-2-yl)phenanthrene

52 g (164 mmol) of 7-bromo(9,9-dimethylfluoren-2-yl)boronic acid (CASNo.: 1213768-48-9), 50 g (164 mmol) of 3-iodophenanthrene and 205 ml ofa 2 M NaHCO₃ aqueous solution (327 mmol) are suspended in 800 ml ofdimethoxyethane. 3.8 g (3.3 mmol) oftetrakis(triphenyl)phosphinepalladium(0) are added to this suspension,and the reaction mixture is heated under reflux for 16 h. After cooling,the organic phase is separated off, filtered through silica gel, washedthree times with 300 ml of water and subsequently evaporated to dryness.Filtration of the crude product through silica gel with heptane/ethylacetate (20:1) gave 55 g (75%) of3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)phenanthrenes.

Biphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenanthren-3-yl-9H-fluoren-2-yl)amines

19.2 g of biphenyl-4-biphenyl-2-ylamine (60 mmol), 26.9 g of3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)phenanthrenes (60 mol) aredissolved in 500 ml of toluene: The solution is degassed and saturatedwith N₂. 3.2 g (3.9 mmol) of a tri-tert-butylphosphine solution and 0.27g (1.2 mmol) of palladium(II) acetate are then added, and 8.9 g ofsodium tert-butoxide (90 mmol) are subsequently added. The reactionmixture is heated at the boil under a protective atmosphere for 4 h. Themixture is subsequently partitioned between toluene and water, theorganic phase is washed three times with water and dried over Na₂SO₄ andevaporated in a rotary evaporator. After filtration of the crude productthrough silica gel with toluene, the residue which remains isrecrystallised from heptane/toluene and finally sublimed in a highvacuum, purity is 99.9%. The yield is 28 g (68% of theory.

Examples 20-22 Synthesis of Compounds (3-2) to (3-4)

The starting compounds are prepared analogously to the synthesisdescribed in Example 18.

Starting Starting material 1 material 2 Product Yield

78%

70%

Compounds (3-2) to (3-4) are prepared analogously to the synthesis ofcompound (3-1) described in Example 19.

Starting material 1 Starting material 2 Product Yield 3-2

65% 3-3

75% 3-4

78%

The comparative compound (V4) is also prepared analogously to thesynthesis of compound (3-1) described in Example 19.

Starting Starting material 1 material 2 Product HTMV4

Examples 23-25 Synthesis of the Compounds(9,9-dimethyl-9H-fluoren-2-yl)-(9,9-diphenyl-9H-fluoren-4-yl)phenanthren-3-ylamine(4-1), (4-2 and (4-3)

(9,9-Dimethyl-9H-fluoren-2-yl)phenanthren-3-ylamine

18.4 g (95.29 mmol) of 3-aminophenanthrene, 26 g (95.4 mmol) of2-bromofluorene and 18.3 g (190 mmol) of sodium tert-butoxide aresuspended in 350 ml of toluene. 1.07 g (4.76 mmol) of palladium acetateand 2.64 g of 1,1-bis(diphenylphosphino)ferrocene (4.76 mmol) are addedto this suspension. The reaction mixture is heated under reflux for 16h. After cooling, the organic phase is separated off washed three timeswith 200 ml of water and subsequently evaporated to dryness. The residueis recrystallised from toluene (31 g, 85% yield).

(9,9-Dimethyl-9H-fluoren-2-yl)-(9,9-diphenyl-9H-fluoren-4-yl)phenanthren-3-ylamine(4-1)

13.1 g of (9,9-dimethyl-9H-fluoren-2-yl)phenanthren-3-ylamine (34 mmol),13.5 g of 4-bromo-9,9-diphenyl-9H-fluorene (34 mol) are dissolved in 300ml of toluene: The solution is degassed and saturated with N₂. 1.4 ml(0.68 mmol) of a 1 M tri-tert-butylphosphine solution and 0.153 g (0.68mmol) of palladium(II) acetate are then added, and 6.5 g of sodiumtert-butoxide (68 mmol) are subsequently added. The reaction mixture isheated at the boil under a protective atmosphere for 4 h. The mixture issubsequently partitioned between toluene and water, the organic phase iswashed three times with water and dried over Na₂SO₄ and evaporated in arotary evaporator. After filtration of the crude product through silicagel with toluene, the residue which remains is recrystallised fromheptane/toluene and finally sublimed in a high vacuum, purity is 99.9%.The yield is 14.3 g (60% of theory).

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield 4-2

65% 4-3

58%

Example 26

Characterisation of the Compounds

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 2004/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials etc.).

The data of various OLEDs are shown in the following examples (seeTables 1 and 2). The substrates used are glass plates coated withstructured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDshave in principle the following layer structure:substrate/hole-injection layer (HIL1)/hole-transport layer(HIL2)/hole-injection layer (HIL3)/electron-blocking layer (EBL)I/emission layer (EML)/electron-transport layer (ETL)/electron-injectionlayer (EIL) and finally a cathode. The cathode is formed by an aluminiumlayer with a thickness of 100 nm. The precise structure of the OLEDs isrevealed by Table 1. The materials required for the production of theOLEDs are shown above.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter), which isadmixed with the matrix material or matrix materials in a certainproportion by volume by coevaporation. An expression such as H1:SEB1(95%:5%) here means that material H1 is present in the layer in aproportion by volume of 95% and SEB1 is present in the layer in aproportion of 5%. Analogously, the electron-transport layer may alsoconsist of a mixture of two materials.

The OLEDs are characterised by standard methods. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in Im/W) and the external quantumefficiency (EQE, measured in percent) as a function of the luminousdensity, calculated from current/voltage/luminous density characteristiclines (IUL characteristic lines) assuming Lambert emissioncharacteristics, and the lifetime are determined. Theelectroluminescence spectra are determined at a luminous density of 1000cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The term EQE @ 1000 cd/m² denotes the external quantumefficiency at an operating luminous density of 1000 cd/m². LT80 @6000cd/m2 is the lifetime by which the OLED has dropped from a luminance of6000 cd/m² to 80% of the initial intensity, i.e. to 4800 cd/m². The dataof the various OLEDs are summarised in Table 2.

Use of Compounds According to the Invention as Matrix Materials inFluorescent OLEDs

Compounds according to the invention are particularly suitable as HIL,HTL or EBL in OLEDs. They are suitable as a single layer, but also asmixed component as HIL, HTL, EBL or within the EML.

Compared with NPB reference components (V1), all samples comprising thecompounds according to the invention exhibit both higher efficienciesand also significantly improved lifetimes in singlet blue.

Compared with the reference material HTMV1-HTMV5 (V2-V6), the compound(1-9), (1-1) and (1-11) according to the invention have betterefficiencies and improved lifetimes. Compared with HTMV6 and HTMV7 (V7and V8), the compound (1-1) according to the invention has asignificantly improved lifetime.

TABLE 1 Structure of the OLEDs IL (5 nm HIL1)/HTL (150 nm HIL2)/IL(5 nmHIL1)/EBL/EML/ETL EBL EML ETL Ex. Thickness/nm Thickness/nm Thickness/nmV1 NPB H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V2 HTMV1H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V3 HTMV2H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V4 HTMV3H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V5 HTMV4H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V6 HTMV5H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V7 HTMV6H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V8 HTMV7H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E0 HTMV8H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E1 (1-9)H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E2 (1-1)H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E3  (1-11)H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E4  (1-12)H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E5 (2-6)H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E6 (1-2)H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E7 (4-1)H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm

TABLE 2 Data of the OLEDs EQE @ 1000 cd/m2 LT80 @ 6000 cd/m² CIE Ex. %[h] x y V1 4.8 70 0.14 0.17 V2 6.4 20 0.13 0.16 V3 5.4 25 0.13 0.15 V46.6 65 0.13 0.15 V5 5.6 80 0.13 0.15 V6 5.0 60 0.13 0.16 V7 6.8 100 0.140.14 V8 6.9 110 0.14 0.15 E0 6.8 115 0.13 0.16 E1 6.7 125 0.13 0.15 E27.0 155 0.13 0.15 E3 6.9 135 0.13 0.15 E4 6.8 120 0.13 0.15 E5 5.0 800.13 0.16 E6 7.1 125 0.13 0.15 E7 7.1 120 0.13 0.15

Example E0 exhibits a significantly improved LT50 value compared withComparative Examples V1 to V8. Further, significant improvementscompared both with the comparative examples and also compared with E0can be achieved by the phenanthrene, apart from position 3, having nofurther aromatic and/or heteroaromatic substitution (E1 to E7). Compound(2-6) (E5) can be compared directly with NPB (V1). It can be seen thatcompound (2-6) results in devices having significantly improved EQEvalues and in particular in improved LT80 values.

The invention claimed is:
 1. A compound of the formula (1)

where the following applies to the symbols and indices occurring: X ison each occurrence, identically or differently, N and CR¹ where amaximum of 2 of the X is optionally equal to N; L is a single bond or adivalent aryl or heteroaryl group having 12 to 40 ring atoms, which isoptionally substituted by one or more radicals R², where, if L is asingle bond, the nitrogen is bonded directly to position 3 of thephenanthrene; Ar¹ is selected from formulae (9)-(28), (20′)-(20″),(29)-(36) (32′)-(34′) and (37)-(100):

where the dashed line represents the bonding position and where thestructures may be substituted by one or more radicals R^(4′), and R^(4′)is on each occurrence, identically or differently, D, F, Cl, Br, I,C(═O)R², CN, Si(R²)₃, NR², NO₂, P(═O)(R²)₂, S(═O)R², S(═O)₂R², astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR² and where one or more CH₂ groups in the above-mentioned groups isoptionally replaced by —R²C═CR²—, Si(R²)₂, C═O, C═S, C═NR², —C(═O)O—,—C(═O)NR²—, P(═O)(R²), —O—, —S—, SO or SO₂ and where one or more H atomsin the above-mentioned groups is optionally replaced by D, F, Cl, Br, I,CN or NO₂, or an aromatic ring system having 6 to 30 aromatic ringatoms, which may in each case be substituted by one or more radicals R²,where two or more radicals R^(4′) is optionally linked to one anotherand may form a ring; Ar² is on each occurrence, identically ordifferently, an aromatic or heteroaromatic ring or an aromatic orheteroaromatic ring system having 5 to 40 aromatic ring atoms, where thering or ring system is optionally substituted by one or more radicalsR⁴, where, if both Ar¹ and also Ar² are phenyl radicals, at least one R⁴on the phenyl radicals is not equal to H and this at least one radicalR⁴ optionally contains one or more aromatic or heteroaromatic rings; R¹is on each occurrence, identically or differently, H, D, F, Cl, Br, I,C(═O)R², CN, Si(R²)₃, NO₂, P(═O)(R²)₂, S(═O)R², S(═O)₂R², astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR² and where one or more CH₂ groups in the above-mentioned groups isoptionally replaced by —R²C═CR²—, —C≡C—, Si(R²)₂, C═O, C═S, C═NR²,—C(═O)O—, —C(═O)NR²—, P(═O)(R²), —O—, —S—, SO or SO₂ and where one ormore H atoms in the above-mentioned groups is optionally replaced by D,F, Cl, Br, I, CN or NO₂, or an aromatic ring system having 6 to 30aromatic ring atoms, which may in each case be substituted by one ormore radicals R², where two or more radicals R¹ is optionally linked toone another and may form a ring; R⁴ is on each occurrence, identicallyor differently, H, D, F, Cl, Br, I, C(═O)R², CN, Si(R²), NR², NO₂,P(═O)(R²)₂, S(═O)R², S(═O)₂R², a straight-chain alkyl, alkoxy orthioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl,alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl oralkynyl group having 2 to 20 C atoms, where the above-mentioned groupsmay each be substituted by one or more radicals R² and where one or moreCH₂ groups in the above-mentioned groups is optionally replaced by—R²C═CR²—, Si(R²)₂, C═O, C═S, C═NR², —C(═O)O—, —C(═O)NR²—, P(═O)(R²),—O—, —S—, SO or SO₂ and where one or more H atoms in the above-mentionedgroups is optionally replaced by D, F, Cl, Br, I, CN or NO₂, or anaromatic ring system having 6 to 30 aromatic ring atoms, which may ineach case be substituted by one or more radicals R², where two or moreradicals R⁴ is optionally linked to one another and may form a ring; R²is on each occurrence, identically or differently, H, D, F, Cl, Br, I,C(═O)R³, CN, Si(R³)₃, NO₂, P(═O)(R³)₂, S(═O)₂R³, S(═O)₂R³, astraight-chain alkyl, alkoxy or thio-alkyl group having 1 to 20 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR³ and where one or more CH₂ groups in the above-mentioned groups isoptionally replaced by — R³C═CR³—, Si(R³)₂, CO, ═C═S, C═NR³, —C(═O)O—,—C(═O)NR³—, P(═O)(R³), —O—, —S—, SO or SO₂ and where one or more H atomsin the above-mentioned groups is optionally replaced by D, F, Cl, Br, I,CN or NO₂, or an aromatic or heteroaromatic ring system having 5 to 30aromatic ring atoms, which may in each case be substituted by one ormore radicals R³, or an aryloxy or heteroaryloxy group having 5 to 30aromatic ring atoms, which is optionally substituted by one or moreradicals R³, where two or more radicals R² is optionally linked to oneanother and optionally form a ring; R³ is on each occurrence,identically or differently, H, D, F or an aliphatic, aromatic orheteroaromatic organic radical having 1 to 20 C atoms, in which, inaddition, one or more H atoms is optionally replaced by D or F; two ormore substituents R³ here is optionally linked to one another andoptionally form a ring; where the compound of the formula (1), besidesthe phenanthrene, contains no further condensed aromatic orheteroaromatic ring having more than 10 ring atoms and where theradicals R¹ on the phenanthrene in formula (1) contain no further aminegroups.
 2. The compound according to claim 1, wherein the compound is ofthe formula (2):

where the definitions from claim 1, apply to the symbols used.
 3. Thecompound according to claim 1, wherein the compound is of the formula(5):

where Q is on each occurrence, identically or differently, CR⁴ or N. 4.The compound according to claim 1, wherein the compound is of theformula (6):

where Q is on each occurrence, identically or differently, CR⁴ or N. 5.The compound according to claim 1, wherein the compound is of the (7):

where Q is on each occurrence, identically or differently, CR⁴ or N. 6.The compound according to claim 1, wherein L is an aromatic ring systemselected from the group consisting of biphenylenes, terphenylenes andthe compounds of the formula (101a) and (101b),

where Y is equal to C(R²)₂, NR², O, Si(R²)₂ or S.
 7. The compoundaccording to claim 6, wherein Y is C(R²)₂ or NR².
 8. The compoundaccording to claim 1, wherein L is a single bond, so that the aminegroup is bonded directly to the phenanthrene.
 9. The compound accordingto claim 1, wherein the compound contains in total at least 26 ringatoms.
 10. The compound according to claim 1, wherein the compoundcontains only one amine group.
 11. A process for the preparation of thecompound according to claim 1 which comprises a one-step Buchwaldcoupling by reaction of a phenanthrene derivative which contains aleaving group with Ar²—NH—Ar¹.
 12. A process for the preparation of thecompound according to claim 1 which comprises a two-step Buchwaldcoupling by stepwise reaction of a phenanthrene derivative whichcontains a leaving group with (1) Ar²—NH₂ and (2) NH₂—Ar¹.
 13. Anoligomer, polymer or dendrimer containing one or more compoundsaccording to claim 1, where the bond(s) to the polymer, oligomer ordendrimer is optionally localized at any positions in formula (1) whichare substituted by R¹, R⁴ or R².
 14. A composition comprising one ormore compounds according to claim 1 and at least one further organicallyfunctional material selected from the group consisting of fluorescentemitters, phosphorescent emitters, host materials, matrix materials,electron-transport materials, electron-injection materials,hole-conductor materials, hole-injection materials, electron-blockingmaterials and hole-blocking materials.
 15. A formulation comprising atleast one compound according to claim 1 and at least one solvent.
 16. Anelectronic device comprising at least one compound according claim 1.17. The electronic device according to claim 16, wherein the device isselected from organic integrated circuits (O-ICs), organic field-effecttransistors (O-FETs), organic thin-film transistors (O-TFTs), organiclight-emitting transistors (O-LETs), organic solar cells (O-SCs),organic optical detectors, organic photoreceptors, organic field-quenchdevices (O-FQDs), light-emitting electrochemical cells (LECs), organiclaser diodes (O-lasers) and organic electroluminescent devices (OLEDs).18. An organic electroluminescent device which comprises the compoundaccording to claim 1 employed in one or more of the following functions:as hole-transport material in a hole-transport or hole-injection layer,as matrix material in an emitting layer, as electron-blocking material,as exciton-blocking material.